Mechanochemical protocol facilitates the generation of arylmanganese nucleophiles from unactivated manganese metal
Rina Takahashi, Pan Gao, Koji Kubota, Hajime Ito
Abstract
The direct synthesis of organomanganese reagents from organic halides and manganese metal remains a challenge. Current solution-based approaches require the preparation of activated manganese (Rieke manganese) or the use of multiple metal additives to promote the insertion of manganese metal into a carbon-halogen bond. Here, we show that a mechanochemical ball-milling protocol facilitates the generation of various arylmanganese nucleophiles from aryl halides and commercially available, unactivated manganese metal without the need for complicated pre-activation processes and metal additives. These manganese-based carbon nucleophiles can be used directly for one-pot addition reactions with various electrophiles and palladium-catalyzed cross-coupling reactions under bulk-solvent-free mechanochemical conditions. Importantly, all experimental operations can be conducted under atmospheric conditions.